Plasticizers are incorporated into a resin (usually a plastic or elastomer) to increase the flexibility, workability, or distensibility of the resin. The largest use of plasticizers is in the production of “plasticized” or flexible polyvinyl chloride (PVC) products. Typical uses of plasticized PVC include films, sheets, tubing, coated fabrics, wire and cable insulation and jacketing, toys, flooring materials such as vinyl sheet flooring or vinyl floor tiles, adhesives, sealants, inks, and medical products such as blood bags and tubing, and the like.
Other polymer systems that use small amounts of plasticizers include polyvinyl butyral, acrylic polymers, nylon, polyolefins, polyurethanes, and certain fluoroplastics. Plasticizers can also be used with rubber (although often these materials fall under the definition of extenders for rubber rather than plasticizers). A listing of the major plasticizers and their compatibilities with different polymer systems is provided in “Plasticizers,” A. D. Godwin, in Applied Polymer Science 21st Century, edited by C. D. Craver and C. E. Carraher, Elsevier (2000); pp. 157-175.
Plasticizers can be characterized on the basis of their chemical structure. The most important chemical class of plasticizers is phthalic acid esters, which accounted for about 85% worldwide of PVC plasticizer usage in 2002. However, in the recent past there has been an effort to decrease the use of phthalate esters as plasticizers in PVC, particularly in end uses where the product contacts food, such as bottle cap liners and sealants, medical and food films, or for medical examination gloves, blood bags, and IV delivery systems, flexible tubing, or for toys, and the like. For these and most other uses of plasticized polymer systems, however, a successful substitute for phthalate esters has heretofore not materialized.
One such suggested substitute for phthalates are esters based on cyclohexanoic acid. In the late 1990's and early 2000's, various compositions based on cyclohexanoate, cyclohexanedioates, and cyclohexanepolyoate esters were said to be useful for a range of goods from semi-rigid to highly flexible materials. See, for instance, WO 99/32427, WO 2004/046078, WO 2003/029339, WO 2004/046078, U.S. Patent Publication No. 2006-0247461, and U.S. Pat. No. 7,297,738.
Other suggested substitutes include esters based on benzoic acid (see, for instance, U.S. Pat. No. 6,740,254, and also co-pending, commonly-assigned, PCT Publication No. WO2009/118261A1, and polyketones, such as described in U.S. Pat. No. 6,777,514; and also co-pending, commonly-assigned, U.S. Patent Application Publication No. 2008-0242895 A1. Epoxidized soybean oil, which has much longer alkyl groups (C16 to C18) has been tried as a plasticizer, but is generally used as a PVC stabilizer. Stabilizers are used in much lower concentrations than plasticizers. Co-pending and commonly assigned U.S. patent application Ser. No. 12/653,744, filed Dec. 17, 2009, discloses triglycerides with a total carbon number of the triester groups between 20 and 25, produced by esterification of glycerol with a combination of acids derived from the hydroformylation and subsequent oxidation of C3 to C9 olefins, having excellent compatibility with a wide variety of resins and that can be made with a high throughput.
U.S. Pat. Nos. 1,909,092 and 2,233,513, both to Brunson and incorporated herein by reference, disclose esters of aryl benzoic acids of the formula R—CO—R′—COOH, wherein R and R′ are aromatic nuclei, including esters derived from saturated monohydric alcohols containing three or more carbon atoms in the molecule, such as iso-propyl, butyl, isoamyl, beta-ethoxyethyl, beta-butoxyethyl, benzyl and cyclohexyl alcohols. The esters are disclosed as useful as plasticizers for nitrocellulose.
U.S. Pat. No. 2,372,947 to Gresham, incorporated herein by reference, discloses polyvinyl halide compositions containing alkyl esters of ortho-benzoyl benzoic acid, wherein the ester group is a C4 to C16 alkyl, such as butyl o-benzoyl benzoate, 2-ethylhexyl o-benzoyl benzoate, lauryl o-benzoyl benzoate, and cetyl o-benzoyl benzoate.
U.S. Pat. No. 3,110,724 to Woodbridge et al., incorporated herein by reference, discloses a process of reacting an aromatic anhydride with another aromatic compound over a catalyst and esterifying the resulting intermediate with a polyalkylene glycol to form surfactants.
Co-pending and commonly owned U.S. Provisional Patent Application Ser. No. 61/227,116, filed Jul. 21, 2009, herein incorporated by reference, discloses the esterification of keto acids derived from the acylation of aromatic compounds with cyclic anhydrides.
Thus what is needed is a method of making a general purpose non-phthalate plasticizer having and providing a plasticizer having suitable melting or chemical and thermal stability, pour point, glass transition, increased compatibility, good performance and low temperature properties.